CN114214027A - Non-gel hardening type alkali glue and preparation method thereof - Google Patents
Non-gel hardening type alkali glue and preparation method thereof Download PDFInfo
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- CN114214027A CN114214027A CN202111610743.7A CN202111610743A CN114214027A CN 114214027 A CN114214027 A CN 114214027A CN 202111610743 A CN202111610743 A CN 202111610743A CN 114214027 A CN114214027 A CN 114214027A
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- alkali glue
- gel
- potassium hydroxide
- gel hardening
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Abstract
The invention belongs to the technical field of alkali glue, and particularly relates to non-gel hardening alkali glue and a preparation method thereof, wherein the molecular structure of the non-gel hardening alkali glue is R1 (Me)2SiO)3+n1SiMe2O‑K+The compound of (1). Wherein R1 is C1‑3Preferably, the R1 group is methyl (Me) or vinyl (Vi). Methyl or vinyl end capping is introduced, hydroxyl end capping is not contained, and the catalyst is used for synthesizing non-hydroxyl end capping polysiloxane, and the hydroxyl end capping is not introduced, so that the quality is higher. The potassium hydroxide alkali glue synthesized by the invention introduces methyl or vinyl end capping, does not contain hydroxyl end capping, does not generate gel hardening phenomenon caused by hydroxyl condensation reaction or siloxane polymerization reaction in the storage process, is used as a catalyst for synthesizing non-hydroxyl end capping polysiloxane, and does not introduceThe hydroxyl is blocked, and the quality is higher.
Description
Technical Field
The invention belongs to the technical field of alkali glue, and particularly relates to non-gel hardening alkali glue and a preparation method thereof.
Background
Because potassium hydroxide is difficult to dissolve in cyclosiloxane, the potassium hydroxide and cyclosiloxane are generally stirred and heated together according to the calculated dosage in a laboratory before polysiloxane is produced and used in production after the potassium hydroxide is completely dissolved.
The potassium hydroxide and the cyclosiloxane disclosed in the Chinese patent with the publication number of CN103613765A are heated and polymerized for a period of time under stirring to prepare the potassium hydroxide alkali glue, the glue can be directly used for production without being prepared, but the storage time is short, and thickening and gelling can occur within 24 hours, thus influencing the use.
Disclosure of Invention
The invention aims to provide a non-gel hardening type alkali glue and a preparation method thereof, and aims to solve the technical problems that the alkali glue in the prior art is short in storage time and can be thickened and gelatinized after being stored for a long time.
In order to achieve the above purpose, the embodiment of the present invention provides a non-gel hardening alkali glue, wherein the molecular structure of the non-gel hardening alkali glue is R1 (Me)2SiO)3+n1SiMe2O-K+A compound of (1); wherein R1 is C1-3Alkyl or alkenyl groups of (a).
Alternatively, the R1 group is methyl or vinyl.
Optionally, the non-gel hardening alkali glue comprises the following raw materials: potassium hydroxide, cyclosiloxane and end-capping reagent, wherein the end-capping reagent has a molecular structure of R2Me2SiO(SiMe2O)n2SiMe2Siloxane of R2.
Alternatively, when the R2 group is methyl, n2 is an integer from 4 to 50.
Alternatively, when the R2 group is vinyl, n2 is an integer from 0 to 50.
Optionally, the non-gel hardening alkali glue comprises the following raw materials: 100 parts by weight of cyclosiloxane, 2-6 parts by weight of potassium hydroxide and 1-5 parts by weight of end-capping reagent.
Optionally, the cyclosiloxane is octamethylcyclotetrasiloxane or a mixture of cyclosiloxanes.
In order to achieve the above object, the preparation method of the non-gel hardening alkali glue provided by the embodiment of the present invention comprises the following steps:
1) adding 100 parts of cyclosiloxane and 2-6 parts of potassium hydroxide into a reaction vessel with a reduced pressure distillation device, a nitrogen pipe and a thermometer, bubbling nitrogen, vacuumizing, stirring and heating;
2) heating the material to 60 deg.C, maintaining the temperature at 60-70 deg.C and vacuum degree above-0.095 MPa, and distilling under reduced pressure for 1-2 hr to remove trace water;
3) closing the vacuum pump, continuously keeping nitrogen bubbling after the vacuum is eliminated by the nitrogen, stirring and heating, and heating the material to 130-140 ℃;
4) after potassium hydroxide is completely dissolved and reacts for 0.5 hour, 1-5 parts of end capping agent is added and the reaction lasts for 1-3 hours;
5) and after the reaction is finished, continuously introducing nitrogen, cooling the reactant to room temperature, and discharging to obtain the non-gel hardening type alkali glue.
The technical scheme or the technical schemes in the non-gel hardening type alkali glue and the preparation method thereof provided by the embodiment of the invention at least have one of the following technical effects:
1. compared with the potassium hydroxide alkali glue produced by the prior art, even if the alkali glue is stored in a sealed manner after being discharged, the appearance of the potassium hydroxide alkali glue changes from transparent to whitish and the viscosity of the potassium hydroxide alkali glue becomes thick within a few hours, and the potassium hydroxide alkali glue can be stored for 24 hours to cause gel hardening and can not be normally used, the potassium hydroxide alkali glue synthesized by the invention can still keep transparent appearance after being stored in a sealed manner for more than 15 days, does not gel and keeps fluidity, and does not influence normal use;
2. the potassium hydroxide alkali glue synthesized by the invention introduces methyl or vinyl end capping, does not contain hydroxyl end capping, does not generate gel hardening phenomenon caused by hydroxyl condensation reaction or siloxane polymerization reaction in the storage process, is used as a catalyst for synthesizing non-hydroxyl end capping polysiloxane, does not introduce hydroxyl end capping, and has higher quality;
3. the potassium hydroxide alkali glue synthesized by the method has low viscosity, good fluidity, more convenient use, better compatibility with cyclosiloxane and easier uniform dispersion.
Detailed Description
The present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
In one embodiment of the invention, a non-gel hardening type alkali glue is provided, and the molecular structure of the non-gel hardening type alkali glue is R1 (Me)2SiO)3+n1SiMe2O-K+The compound of (1). Wherein R1 is C1-3Preferably, the R1 group is methyl (Me) or vinyl (Vi). Methyl or vinyl end capping is introduced, hydroxyl end capping is not contained, gel hardening phenomenon caused by hydroxyl condensation reaction or siloxane polymerization reaction can not occur in the storage process, the catalyst is used for synthesizing non-hydroxyl end capping polysiloxane, hydroxyl end capping is not introduced, and the quality is higher.
In the embodiment of the invention, the non-gel hardening alkali glue comprises the following raw materials: potassium hydroxide, cyclosiloxane and end-capping reagent, wherein the molecular structure of the end-capping reagent is R2Me2SiO(SiMe2O)n2SiMe2Siloxane of R2.
Preferably, when the R2 group is methyl, n2 is an integer from 4 to 50.
Preferably, when the R2 group is vinyl, n2 is an integer from 0 to 50.
Specifically, the non-gel hardening alkali glue comprises the following raw materials: 100 parts by weight of cyclosiloxane, 2-6 parts by weight of potassium hydroxide and 1-5 parts by weight of end-capping reagent.
In the present examples, the cyclosiloxane is octamethylcyclotetrasiloxane (D4) or a mixture of cyclosiloxanes (DMC).
The embodiment of the invention also provides a preparation method of the non-gel hardening type alkali glue, which comprises the following steps:
1) 100 parts of cyclosiloxane and 2-6 parts of potassium hydroxide are added into a reaction vessel with a reduced pressure distillation device, a nitrogen pipe and a thermometer, nitrogen is bubbled, and the reaction vessel is vacuumized and stirred while being heated.
2) Heating the material to 60 deg.C, maintaining the temperature at 60-70 deg.C and vacuum degree above-0.095 MPa, and distilling under reduced pressure for 1-2 hr to remove trace water in the material.
3) The vacuum pump is closed, the nitrogen bubbling is continuously kept after the vacuum is eliminated, the temperature is raised while stirring, and the temperature of the material is raised to 130-.
4) And after the potassium hydroxide is completely dissolved and reacts for 0.5 hour, adding 1-5 parts of end capping agent, and reacting for 1-3 hours.
5) And after the reaction is finished, continuously introducing nitrogen, cooling the reactant to room temperature, and discharging to obtain the non-gel hardening type alkali glue.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. The raw materials used in the examples of the present invention were all obtained commercially.
Example 1
1) Adding 250g of octamethylcyclotetrasiloxane and 5g of potassium hydroxide into a three-neck round-bottom flask with a reduced pressure distillation device, a nitrogen pipe and a thermometer, bubbling nitrogen, vacuumizing, stirring and heating;
2) heating the material to 60 deg.C, maintaining the temperature at 60-70 deg.C and vacuum degree above-0.095 MPa, and distilling under reduced pressure for 1 hr to remove trace water;
3) after dehydration is finished, the vacuum pump is closed, nitrogen bubbling is continuously kept after the vacuum is eliminated, the temperature is raised while stirring, and the temperature of the material is raised to 130-;
4) after potassium hydroxide is completely dissolved and reacts for 0.5 hour, 2.5g of tetramethyl divinyl disiloxane is added and the reaction is carried out for 3 hours;
5) and after the reaction is finished, continuously introducing nitrogen, cooling the reactant to room temperature, discharging, sealing and storing to obtain the colorless transparent non-gel hardened potassium hydroxide alkali glue.
Example 2
1) Adding 250g of octamethylcyclotetrasiloxane and 4g of potassium hydroxide into a three-neck round-bottom flask with a reduced pressure distillation device, a nitrogen pipe and a thermometer, bubbling nitrogen, vacuumizing, stirring and heating;
2) heating the material to 60 deg.C, maintaining the temperature at 60-70 deg.C and vacuum degree above-0.095 MPa, and distilling under reduced pressure for 1 hr to remove trace water;
3) after dehydration is finished, the vacuum pump is closed, nitrogen bubbling is continuously kept after the vacuum is eliminated, the temperature is raised while stirring, and the temperature of the material is raised to 130-;
4) after potassium hydroxide is completely dissolved and reacts for 0.5 hour, 4g of polydimethylsiloxane with the viscosity of 5cs is added and the reaction lasts for 2 hours;
5) and after the reaction is finished, continuously introducing nitrogen, cooling the reactant to room temperature, discharging, sealing and storing to obtain the colorless transparent non-gel hardened potassium hydroxide alkali glue.
Comparative example
1) Adding 250g of octamethylcyclotetrasiloxane into a three-neck round-bottom flask with a reduced pressure distillation device, a nitrogen pipe and a thermometer, vacuumizing, stirring and heating;
2) heating the material to 60 deg.C, vacuumizing, introducing nitrogen gas, keeping the material temperature at 60-70 deg.C and vacuum degree above-0.05 MPa, and dehydrating under reduced pressure for 1 hr;
3) after dehydration, closing the vacuum pump, stopping nitrogen bubbling after the vacuum of the nitrogen is eliminated, adding 4g of potassium hydroxide, stirring and heating, and heating the material to 140 ℃;
4) after potassium hydroxide is dissolved, carrying out polymerization reaction for 3 hours;
5) cooling the reactant to room temperature, discharging to obtain hydrogen-oxidant alkali glue, and sealing and storing the product with slightly hazy appearance.
The potassine hydroxide gels prepared in examples 1 and 2 and comparative examples were tested for storage and the test structures are shown in Table 1.
TABLE 1
As can be seen from Table 1, compared with the comparative alkali glue, even if the alkali glue is stored in a sealed manner after being discharged, the appearance of the alkali glue becomes cloudy white from transparent within a few hours, the viscosity of the alkali glue becomes thick, and the gel is hardened after being stored for 24 hours, so that the alkali glue can not be normally used, the potassium hydroxide glue synthesized by the invention can still keep transparent appearance after being stored in a sealed manner for more than 15 days, does not gel, keeps fluidity, and does not influence normal use. The potassium hydroxide alkali glue synthesized by the method has low viscosity, good fluidity, more convenient use, better compatibility with cyclosiloxane and easier uniform dispersion.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The non-gel hardening type alkali glue is characterized in that the molecular structure of the non-gel hardening type alkali glue is R1 (Me)2SiO)3+n1SiMe2O-K+A compound of (1); wherein R1 is C1-3Alkyl or alkenyl groups of (a).
2. The non-gel hardening alkali glue of claim 1, wherein the R1 group is methyl or vinyl.
3. The non-gel hardening alkaline gum as claimed in claim 2, characterized by comprising the following raw materials: potassium hydroxide, cyclosiloxane and end-capping reagent, wherein the end-capping reagent has a molecular structure of R2Me2SiO(SiMe2O)n2SiMe2Siloxane of R2.
4. The non-gel-hardening type alkali glue according to claim 3, wherein when the R2 group is a methyl group, n2 is an integer of 4 to 50.
5. The non-gel-hardening type alkali glue according to claim 3, wherein when the R2 group is a vinyl group, n2 is an integer of 0 to 50.
6. The non-gel hardening alkaline gum as claimed in claim 3, characterized by comprising the following raw materials: 100 parts by weight of cyclosiloxane, 2-6 parts by weight of potassium hydroxide and 1-5 parts by weight of end-capping reagent.
7. The non-gel hardening alkaline gum according to any one of claims 3-6, wherein the cyclosiloxane is octamethylcyclotetrasiloxane or a mixture of cyclosiloxanes.
8. The method for preparing a non-gel hardening alkaline gum according to any one of claims 1 to 7, comprising the steps of:
1) adding 100 parts of cyclosiloxane and 2-6 parts of potassium hydroxide into a reaction vessel with a reduced pressure distillation device, a nitrogen pipe and a thermometer, bubbling nitrogen, vacuumizing, stirring and heating;
2) heating the material to 60 deg.C, maintaining the temperature at 60-70 deg.C and vacuum degree above-0.095 MPa, and distilling under reduced pressure for 1-2 hr to remove trace water;
3) closing the vacuum pump, continuously keeping nitrogen bubbling after the vacuum is eliminated by the nitrogen, stirring and heating, and heating the material to 130-140 ℃;
4) after potassium hydroxide is completely dissolved and reacts for 0.5 hour, 1-5 parts of end capping agent is added and the reaction lasts for 1-3 hours;
5) and after the reaction is finished, continuously introducing nitrogen, cooling the reactant to room temperature, and discharging to obtain the non-gel hardening type alkali glue.
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